Air-Stable Boranes and Borinanes Encapsulated in Organogels for Anionic Ring-Opening (Co)Polymerization

Organoborane reagents play a pivotal role as Lewis acids in acid-base pairs used in anionic polymerization and in other reactions; yet their high sensitivity to oxygen and moisture necessitates effective stabilization to prevent their oxidation and thus maintain their catalytic activity. In this study, we present novel encapsulation methods employing a cost-effective hexatriacontane (C₃₆H₇₄, C36) organogel to stabilize sensitive organoborane reagents, including triethyl borane (TEB) and a borinane-based ammonium salt (B₃NBr). These organoboranes encapsulated in stable, self-standing organogel blocks enable their safe handling in open laboratory environments without the need for a glovebox. Upon heating such borane-containing organogel blocks organoboranes could be freed from the organogel and used to mediate both the homopolymerization of propylene oxide (PO) and the copolymerization of PO with CO₂. Furthermore, efficient recovery of the C36 gelator from polymerization mixtures is achieved, with mass recovery ranging from 70 % to 90 %. This encapsulation method offers a practical and efficient solution for stabilizing, storing, and handling highly reactive organoborane reagents, thereby broadening their applicability and utilization in various chemical transformations.